Heterobimetallic Chalcogenide Cluster Polymers: Synthesis, Structures And Third-order Nonlinear Optical Properties

The dissertation focuses on the synthesis and structures of polymeric Mo(W)/S/Cu(Ag) clusters, twenty new Mo(W)/S/Cu(Ag) polymers have been prepared and structurally characterized, of which two are 0-D, thirteen are 1-D, one are 2-D and four are 3-D polymers. The third-order nonlinear optical (NLO) properties of twelve synthesized compounds were investigated.1. Single-bridged strategy had been studied for the generation of multidimensional Mo(W)/S/Cu clusters. Through single cyanide bridges, a novel 3-D W/S/Cu heterobimetallic cluster with a heavily-distorted diamondoid topology was constructed from the T-shaped building clusters [WS₄Cu₃]⁺, its third-order NLO properties had been characterized.2. The construction of Mo(W)/S/Cu clusters with nondefault nets had been explored. 2,6-lutidine as sterically constraining ligand was selected to synthesize Mo(W)/S/Cu clusters with non-default nets, which gave rise to an novel 3-D W/S/Cu cluster showing lcv topology and strong third-order NLO properties; lcv topology has not been reported thus far.3. Two pillar-layered 3-D Mo(W)/S/Cu clusters were constructed by nest-shaped building clusters [MOS₃Cu₃]⁺ in the presence of 1,2-Di(4-pyridyl)ethylene. The 3-D W/S/Cu cluster shows very strong third-order NLO properties.4. Three novel Mo(W)/S/Ag clusters were synthesized in the presence of Sr(NO₃)₂. Two of them show octanuclear square-like frameworks; another one exhibits an unusual double-chain structure. Their third-order NLO properties were studied.5. Cation-directing synthesis of polymeric W/S/Ag clusters had been studied. Three polymeric W/S/Ag clusters with different structures had been synthesized by the reactions of (NH₄)₂WS₄, AgI and Yb(NO₃)₃ in different solvents; at the same time three polymeric W/S/Ag clusters with same structures had been constructed in same solvents containing different rare-earth metal cations.6. Four polymeric Mo(W)/S/Ag clusters with rare-earth metal cations were synthesized and their third-order NLO properties were characterized.